Block polymers of polyphenylene oxide and polystyrene

ABSTRACT

Linear, branched and/or cross-linked block polymers of polyphenylene oxides and polystyrene are described. The polyphenylene oxide-polystyrene block polymers can be molded, calendered, or extruded as films, sheets, fibers, laminates or other useful articles of manufacture.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention is related to subject matter disclosed in copending U.S.Ser. Nos. 800,635, 800,648, and 800,656 all filed May 26, 1977; 907,596filed May 19, 1978; Ser. Nos. 916,761 and 916,763 both filed June 19,1978; U.S. Pat. No. 4,140,675 issued Feb. 20, 1979 and U.S. Pat. No.4,146,697 issued Mar. 27, 1979. All of the aforesaid applications areassigned to the assignee of this application and all of the subjectmatter disclosed and referenced therein is incorporated herein in itsentirety by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to linear, branched, and/or cross-linked blockpolymers of polyphenylene oxides and polystyrenes. The polyphenyleneoxide-polystyrene block polymers can be molded, calendered, or extrudedas films, sheets, fibers, laminates or other useful articles ofmanufacture.

In my copending U.S. applications Ser. No. 800,635 new quinone-coupledto polyphenylene oxide polymers having an average hydroxyl group permolecule value greater than zero including 2.0 or less, and Ser. No.907,596 and U.S. Pat. No. 4,146,697 new polyfunctional styrene polymershaving telechelic organosiloxy and/or hydroxy functional groups,respectively, are described. The new polyfunctional quinone-coupledpolyphenylene oxides either alone or in combination with monofunctionalpolyphenylene oxides of the prior art, i.e., polyphenylene oxides havingan average hydroxyl group per molecule value greater than zero including1.0 or less, or combinations thereof can be coupled with the newpolyfunctional polystyrenes to form new linear, branched, and/orcross-linked polyphenylene oxide-polystyrene block polymers.

2. Description of the Prior Art

Self-condensation reactions of certain phenols employing oxygen incombination with an effective oxidative coupling catalyst system to formmonofunctional prior art polyphenylene oxides, i.e., polyphenyleneoxides having an average hydroxyl group per molecule of 1.0 or less, arewell-known and are described in various publications including Hay'sU.S. Pat. Nos. 3,306,879; 3,914,266; 4,028,341, a continuation-in-partof Ser. No. 441,295, filed Feb. 11, 1974, now abandoned; Olander's U.S.Pat. Nos. 3,956,442; 3,965,069; 3,972,851 and 4,054,553, among manyothers.

DESCRIPTION OF THE INVENTION

This invention embodies linear, branched, and/or cross-linked blockpolymers of polyphenylene oxides and polystyrenes. The polyphenyleneoxide-polystyrene block polymers can be molded, calendered, or extrudedas films, sheets, fibers, laminates or other useful articles ofmanufacture.

In general, illustrative of the broad group of linear, branched andcross-linked polyphenylene oxide-polystyrene block polymers that areincluded within the scope of this invention are those described, amongothers, by the following model structures:

    __________________________________________________________________________    (I linear)                                                                            AZC, BZC, AZCZA, AZCZB, BZCZB, AZCZBZCZA,                                     AZCZBZCZCZB, etc., etc., etc.                                          (I branched)                                                                          ##STR1##                                                              (I cross-linked)                                                                      ##STR2##                                                             __________________________________________________________________________

The above illustrative linear, branched, and cross-linked combinationsof polyfunctional polyphenylene oxide and polyfunctional polystyreneunits, including monofunctional polyphenylene oxides and combinationsthereof, including random and/or alternating arrangements of polymerunits defined by the units A, B, C, or coupling agent Z--which units andcoupling agents are described in greater detail hereafter--are notintended to limit the combinations that can be obtained by the practiceof this invention since the block polymer combinations of this inventionare limited only by the amount of block polymer precursors charged tothe reaction medium in carrying out the process of this invention.Presently preferred block polymers of polyphenylene oxide andpolystyrene are linear block polymers wherein the coupling agent of thepolymer backbone is a bifunctional coupling agent. Even more preferredare linear polymers containing substantial amounts of polystyrene units,i.e. amounts sufficient to provide polystyrene segments which comprisefrom about 20 to about 80 percent by weight of the total weight of blockpolymer.

In general, the expression "monofunctional polyphenylene oxides" asemployed herein and in the claims includes polyphenylene oxides havingan average hydroxyl group per molecule value greater than zero including1.0 or less. These polyphenylene oxides can be prepared by any of themethods of the prior art, and can be described by formula (II) set outhereafter: ##STR3## wherein independently each R is hydrogen, ahydrocarbon radical, a halohydrocarbon radical, a hydrocarbonoxy radicalor a halohydrocarbonoxy radical, n is a number of at least 1, preferably10, and more preferably 40 to 170, and m being a number average of from0.001 to about 1.0. The monofunctional polyphenylene oxide units of theblock polymers can be conceptualized by the structure of formula (I)above wherein the hydrogen atom is disassociated from the monohydroxygroup of the polyphenylene oxide, e.g. where m is zero. When m is zero,the radical of formula (II) can be described as a phenoxy radical, amonovalent phenoxy residue and can be abbreviated by the formula --A.

In general, the expression "polyfunctional polyphenylene oxides" asemployed herein and in the claims includes quinone-coupled polyphenyleneoxides having an average hydroxyl group per molecule greater than zeroincluding 2.0 or less. These polyphenylene oxides can be prepared by themethods described in U.S. application Ser. Nos. 800,635 and 800,646, andcan be described by the formula (III) set out hereafter: ##STR4##wherein independently each --OEO-- is a divalent quinone residue, E is adivalent arene radical, either a or b is at least equal to 1, the sum ofa plus b is preferably at least equal to 10, more preferably 40 to 170,the sum of r and s being a number average of from about 0.001 to about2.0, R is the same as in formula (I) above. The polyfunctionalpolyphenylene oxide units of the block polymers can be conceptualized bythe structure of formula (III) above wherein the hydrogen atoms aredisassociated from the polyhydroxy groups of the quinone-coupledpolyphenylene oxide, e.g. where r and s are equal to zero. When r and sare zero the radical of formula (III) can be described asquinone-coupled polyphenoxy radical, a divalent phenoxy radical, and canbe abbreviated by the formula --B--.

In general, the expression "polyfunctional polystyrene" as employedherein and in the claims includes polystyrenes having an averagehydroxyl or siloxy group per molecule value greater than zero including2 or more. The polystyrenes can be prepared by the methods disclosed inmy copending applications Ser. No. 907,596 and U.S. Pat. No. 4,146,697and can be described by formula (IV) set out hereafter: ##STR5## whereinindependently each x is an integer at least equal to 1 and is a maximumequal to the number of replaceable hydrogen atoms associated with the R"arene radical, y is an integer at least equal to 1, R' is hydrogen or anorganosilyl group, i.e. (R'''₃ --Si--, R''' being an alkyl, cycloalkyl,or aryl radical including combinations thereof, R" is at least adivalent arene radical having at least one (R'O-- radical directlybonded to an aromatic ring carbon atom via an oxygen atom, Q is ahydrogen, halogen, alkyl or alkenyl radical, p is an integer of from 1to 5, and z is an integer at least equal to 2, preferably 10 to 500, andmore preferably 50 to 300. The polyfunctional polystyrene units of theblock polymers can be conceptualized by the structure of formula (IV)above wherein the hydrogen or silyl group is disassociated from theoxygen atom. When the R' group is disassociated, the radicals of formula(IV) can be described as polystyrene having polyfunctional phenoxyradical end groups and can be abbreviated by the formula --C--. Althoughin formula (IV) above the recurring styrenic monomeric units areillustratively described as follows: ##STR6## wherein Q, p and z are asdefined hereinbefore, the term "polystyrene" as used herein and in theclaims includes any of the well-known homo- or copolystyrene types, e.g.styrene-acylonitrile; styrene-butadiene-acrylonitrile;styrene-butadiene; styrene-divinyl benzene; styrene-maleic anhydride;styrene-methyl methacrylate; styrene-vinyl acetate; styrene-isoprene,etc.

In general, the expression coupling agents as employed herein and in theclaims includes "polyacyl halides", e.g. acyl halides having at leasttwo halide coupling reaction sites. These acyl halides can be describedby the formula (V) set out hereafter: ##STR7## wherein c is a number atleast equal to 2, X is a halogen, e.g. fluorine, chlorine, bromine oriodine, preferably chlorine, and R'''' is C₁₋₈ alkylene, C₁₋₈alkenylene, phenylene, halophenylene and C₁∝8 alkyl substitutedphenylene. The coupling agents of the block polymers can beconceptualized by the structure of formula (V) above wherein the halogenatoms are disassociated from the acyl halides. These radicals areabbreviated herein by the symbol --Z--, or ##STR8##

Illustrative of a portion of presently preferred acyl halides are theacid halides of the following acids: malonic, succinic, maleic, fumaric,itaconic, mesaconic, citraconic, glutaric, adipic, pimelic, suberic,azelaic, trimellitic, phthalic, isophthalic, terephthalic and the abovephthalic acids having from one to four halogens, preferably chlorosubstituents or from one to four C₁₋₈ alkyl substituents. The mostpreferred phthalic acid halides are unsubstituted and have two chlorinesubstituents, e.g. isophthaloyl chloride.

In general, the process of preparing polyphenylene oxide-polystyreneblock polymers comprises contacting mono and/or polyfunctionalpolyphenylene oxides, polyfunctional polystyrenes and coupling agents inthe presence of an aqueous solution of a water soluble base and acatalytic phase transfer agent. Any amount of functional (reactive)polyphenylene oxides, polystyrenes and coupling agent can be employed,e.g. from 1/1000 to 1000 times the stoichiometric requirements requiredto completely couple all of the reactive polyphenylene oxide andpolystyrene.

Any water soluble base can be employed, however preferably is an aqueoussolution of a water soluble base, e.g. an aqueous alkaline metal oralkaline earth metal hydroxide or carbonate solution. Specific examplesinclude aqueous solutions of potassium hydroxide, sodium hydroxide,sodium monocarbonate, barium carbonate, etc. Any amount of water solublebase (WSB) can be employed. Generally effective mole proportions of WSBrelative to the amount of coupling agent that are employed are couplingagent:water soluble base proportions of from about 1:100 to about 50:1and more frequently from about 1:10 to about 10:1.

Any catalytic phase transfer agent can be employed, however, preferablyis a phase transfer agent selected from the group consisting ofquaternary ammonium, quaternary phosphonium, and tertiary sulfoniumcompounds or mixtures thereof. These catalytic phase transfer agents canbe described by the formulas: ##STR9## wherein each R_(a) isindependently selected from aliphatic hydrocarbon radicals having fromabout 1 to about 30 carbon atoms, preferably from about 2 to about 15carbon atoms, each Y⁻ is selected from the group consisting of Cl⁻, Br⁻,F⁻, CH₃ SO₃ ⁻, CH₃ CO₂ ⁻, CF₃ CO₂ ⁻ or OH⁻, and each Y⁻⁻ is selectedfrom the group consisting of SO₄ ⁻⁻, CO₃ ⁻⁻, or C₂ O₄ ⁻⁻. Any amount ofcatalytic phase transfer agent (PTA) can be employed, however generallyeffective molar proportions of PTA relative to the amount of watersoluble base are within the range of from about 1:10 to about 1:1000 andmore frequently within the range of from 1:100 to 1:1000.

The coupling reactions can be carried out at any temperature. Preferablytemperatures within the range of from 0° to 150° C. or even higher, andmore preferably from 50° C. to 100° are employed.

In order that those skilled in the art may better understand myinvention, the following examples are given which illustrate the bestmode of practicing my invention.

EXAMPLE I--PREPARATION OF QUINONE-COUPLED POLYPHENYLENE OXIDE (A)Polymer Preparation, and (B) Catalyst Deactivation

A 2.5 gallon stainless steel reactor equipped with an air-driven paddlestirrer, oxygen inlet tube, and water-cooled coil and jacket was chargedwith 150 g. 2,6-xylenol, 2.3 liters of toluene, 1.5 g. of Adogen® 464,i.e. trialkyl (C₈₋₁₀) methyl ammonium chloride, 3.4 g.N,N'-di-t-butylethylenediamine (DBEDA), 47.5 g. dimethyl-n-butylamine(DMBA), and 15 g. di-n-butylamine (DBA), and 4.2 ml. of a catalyst stocksolution formed by dissolving 19.30 g. of cuprous oxide in 500 ml. of achilled 47.2% aqueous hydrobromic acid solution. Oxygen was bubbledthrough the reaction medium at a rate of 8.3 moles per hour and themixture was stirred vigorously. 1350 g. of 2,6-xylenol in 1.5 liters oftoluene was pumped into the reactor while the reaction temperature wasmaintained at 25°±1° C. over a 30-minute period. The temperature wasthen allowed to rise to 35°±1° C. After the desired reaction productviscosity was obtained the reactor was purged of oxygen by passingnitrogen instead of oxygen through the reaction medium and a 38% aqueoussolution of a trisodium salt of ethylenediamine tetracetic acid (EDTA)was added to deactivate the catalyst system. Summarily, the reactionparameters relative to molar ratios of 2,6-xylenol:Cu:DBEDA:DMBA:Br:DBAwere as follows: 1124:1:1:8:43:3.2:1.

    ______________________________________                                        Summary of Reaction Parameters and                                            Properties of Poly(2,6-dimethyl-1,4-phenylene oxide)                                         React.   React.        OH                                      Run   TMDQ     Temp.    Time   [η]                                                                              Absorbance                              No.   (%)      (°C.)                                                                           (min.) dl./g.)                                                                              @ 3610cm.sup.-1                         ______________________________________                                        1     0.92     25-35    88.5   0.29   0.278                                   ______________________________________                                    

(C) Quinone Coupling

The reaction mixture as described in sections (A) and (B) above with asteady nitrogen sweep was heated to 50° C. and maintained at 50°-55° C.until the deep orange TMDQ color disappeared leaving a very light greensolution. The resulting quinone-coupled polyphenylene oxide wasprecipitated by addition of 3 volumes of methanol, collected byfiltration and dried at 90° C. in an air-circulating oven overnight.

    ______________________________________                                        Summary of Reaction Parameters and                                            Properties of                                                                 Quinone-Coupled Poly(2,6-dimethyl-1,4-phenylene oxide)                                       React.   React.        OH                                      Run   TMDQ     Temp.    Time   [η]                                                                              Absorbance                              No.   (%)      (°C.)                                                                           (min.) (dl./g.)                                                                             @ 3610cm.sup.-1                         ______________________________________                                        1     <0.001   50-55    60     0.24   0.403                                   ______________________________________                                    

EXAMPLE II--PREPARATION OF BIS(4-TRIMETHYLSILOXYPHENYL)DISULFIDE

Hexamethyldisilazane (19.4 gms., 0.12 mole) was added to solidbis(4-hydroxyphenyl)disulphide (20 gms., 0.08 mole). The reaction beganimmediately giving a clear liquid. After 4 hours excesshexamethyldisilazane was removed by warming and evaporation. Gaschromatography showed no starting disulfide and only a trace ofmono-hydroxy disulfide. The liquid product crystallized on cooling at 5°C. m.p. 21°-22°. The ¹ H nmr was consistent with a disilylated disulfideof the formula: ##STR10##

EXAMPLE III--PREPARATION OF POLY(TRIMETHYLSILOXY)TELECHELIC STYRENEPOLYMER

Styrene (100 gms., 0.96 mole, freshly distilled), azobisisobutyronitrile(0.05 gms.) and bis(4-trimethylsiloxyphenyl) disulfide (5.83 gms., 0.15mole) were heated under nitrogen in a 4 oz. screw-cap bottle for sevendays at 50°±3° C. The clear viscous liquid was diluted with toluene andprecipitated by adding to 500 ml. methanol containing a solution of 2gms. calcium nitrate in 50 ml. ethanol in a stirred blender. The polymerwas filtered off, dried, and reprecipitated as above, then dried,redissolved in toluene and precipitated by dropwise addition into 3 l.of methanol containing 1 ml. conc. hydrochloric acid. After filteringand drying, the polymer weighed 50.4 gms., exhibited an intrinsicviscosity (measured in chloroform at 25° C.) of 0.20 dl./g., and aninfrared OH absorbance at 3590 cm.⁻¹ of 0.238 (500 mg./10 ml. CS₂). Thepolymer formula follows: ##STR11## z being a number average of withinthe range of from about 150 to 250.

    ______________________________________                                        Summary of Reaction Parameters and Properties of                              Poly(trimethylsiloxy)telechelic Styrene Polymer                                      React.    React.            OH                                         Run    Temp.     Time      [η] Absorbance                                 No.    (°C.)                                                                            (days)    (dl./g.)                                                                              @ 3590cm.sup.-1                            ______________________________________                                        1      50        7         0.23    0.24                                       ______________________________________                                    

EXAMPLE IV--ACYL-COUPLED BLOCK POLYMERS OF POLYPHENYLENE OXIDE ANDPOLYSTYRENE

A 300 ml. jacketed Waring blender equipped with a nitrogen inlet--inorder to provide an inert nitrogen purged reaction medium, athermocouple--located in the high fluid shear stress reaction region,and septum port was charged with 14 ml. monochlorobenzene, 2 g. ofα,ω-(bis-4-trimethylsiloxyphenylthio)polystyrene prepared as in ExampleIII and 2 g. of quinone-coupled polyphenylene oxide prepared as inExample I. Water at 45° C. was circulated through the blender jacket. Asolution (0.2 ml.) containing 10% Aliquat® 336, i.e.tricaprylmonomethylammonium chloride in toluene, was charged to theblender followed by 0.2 ml. of a 50% aqueous solution of NaOH. Afterhigh speed mixing for 2 minutes, isophthaloyl chloride was added as asolid over a 2-minute period. High shear reaction conditions weremaintained throughout the addition of isophthaloyl chloride and for 2minutes thereafter.

The resulting reaction mixture was diluted with toluene and slowlypoured into a larger blender containing several volumes of methanol. Theblock polymer product was collected by filtration, washed and driedovernight in vacuo at 60° C.

    ______________________________________                                        Summary of Reaction Parameters and Properties of                              Acyl-Coupled Block Polymers                                                          React.    React.            OH                                         Run    Temp.     Time      [η] Absorbance                                 No.    (°C.)                                                                            (min.)    (dl./g.)                                                                              @ 3610                                                                              @ 3590                               ______________________________________                                        1      45        4         0.51    0.01  0.01                                 ______________________________________                                    

A brief resume of the analysis of the resulting block polymer follows:

A sample of the block polymer (0.50 g.) was dissolved in 10 ml. ofmethylene chloride. The solution was stored at 2° C. for 2 days. Apolymer:methylene chloride complex precipitate formed which was formedby filtration at 2° C. The precipitate was then heated to separate themethylene chloride from the polymer by evaporation. The polymerseparated from the polymer:methylene chloride complex, weighed 0.43 g.and contained based on IR analysis 58% by weight of polyphenylene oxideand 42% by weight of polystyrene. Analysis of the filtrate afterevaporation of the methylene chloride established the presence of aresidue containing 17% polyphenylene oxide and 83% polystyrene. On thebasis of these results at least 72% of the initial polystyrene chargedto the reaction medium was calculated as having been incorporated intoan acyl-coupled polyphenylene oxide-polystyrene block polymer.

The conclusion that an acyl-coupled polyphenylene oxide-polystyreneblock polymer was formed was based on the following evidence: theresulting polymer (1) initially dissolved in methylene chloride at 25°C., and (2) subsequently formed an insoluble methylene chloride:polymercomplex which precipitated from solution, and (3) the precipitate wasidentified by IR data as containing both quinone-coupled polyphenyleneoxide and polystyrene polymer segments. Of the polymer precursorsegments, only the quinone-coupled polyphenylene oxide forms aninsoluble methylene chloride complex. Accordingly, based on IR dataidentifying that a polymer containing both polyphenylene oxide andpolystyrene segments were associated with the polymer:methylene chloridecomplex, it was concluded that an acyl-coupled polyphenyleneoxide-polystyrene block copolymer had in fact been formed.

The formation of a methylene chloride complex with polyphenylene oxideis well-known to those skilled in the art as illustrated by A. Factor'sU.S. Pat. No. 3,644,227, issued Feb. 22, 1972 and A. Factor et al.'spublication in Polymer Letters 7, 205 (1969).

The polyphenylene oxide polystyrene block polymers of this invention canbe molded, calendered, or extruded as films, sheets, fibers, laminatesor other useful articles of manufacture.

I claim:
 1. An acyl-coupled block polymer comprising a polyvalent acylradical, a divalent quinone-coupled polyphenoxy radical, and a divalentbis(oxyarylenethio)polystyrene radical.
 2. An acyl-coupled blockcopolymer comprising an acyl radical of the formula ##STR12## wherein cis a number at least equal to 2, and R'''' is C₁₋₈ alkylene, C₁₋₈alkenylene, phenylene, halophenylene and C₁₋₈ alkyl substitutedphenylene; a quinone-coupled polyphenoxy radical of the formula##STR13## wherein independently each --OEO-- is a divalent quinoneresidue, E is a divalent arene radical, either a or b is at least equalto 1, the sum of a plus b is at least equal to 10, and R is hydrogen, ahydrocarbon radical, a halohydrocarbon radical, a hydrocarbonoxy radicalor a halohydrocarbonoxy radical, and a polyfunctional polystyreneradical of the formula ##STR14## wherein independently each x is aninteger at least equal to 1 and is a maximum equal to the number ofreplaceable hydrogen atoms associated with the R" arene radical, y is aninteger at least equal to 1, R" is at least a divalent arene radical, Qis a hydrogen, halogen, alkyl or alkenyl radical, p is an integer offrom b 1 to 5, and z is an integer at least equal to
 2. 3. The claim 2compound, wherein R'''' and R" are phenylene, and --OEO-- is of theformula: ##STR15## wherein independently each R is as definedhereinbefore.
 4. The claim 3 compound, wherein c is equal to 2, the sumof a plus b is 40 to 170, both x and y are equal to 1, and z is 2 to1000.
 5. The claim 2, 3 or 4 compound, wherein each R is hydrogen,hydrocarbon or a halohydrocarbon radical.
 6. The claim 5 compound,wherein each R is a methyl radical.
 7. A process of forming anacyl-coupled polymer which comprises contacting a polyacylhalide, aquinone-coupled polyphenylene oxide having an average hydroxyl group permolecule value greater than zero including 2.0 or less, and apolyfunctional polystyrene selected from the class consisting of abis(hydroxyarylenethio)polystyrene or abis(organosiloxyarylenethio)polystyrene.
 8. The claim 7 process, whereinthe acyl halide is of the formula: ##STR16## where c is a number atleast equal to 2, X is fluorine, chlorine, bromine or iodine, and R" isC₁₋₈ alkyl substituted phenylene, and the polyfunctional polyphenyleneoxide is of the formula: ##STR17## wherein independently each --OEO-- isa divalent quinone residue, E is a divalent arene radical, either a or bis at least equal to 1, the sum of a plus b is at least equal to 10, andR is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, ahydrocarbonoxy radical or a halohydrocarbonoxy radical, and thepolyfunctional polystyrene of the formula: ##STR18## whereinindependently each x is an integer at least equal to 1 and is a maximumequal to the number of replaceable hydrogen atoms associated with the R"arene radical, y is an integer at least equal to 1, R' is hydrogen or anorganosilyl group, R" is at least a divalent arene radical having atleast one (R'O-- radical directly bonded to an aromatic ring carbon atomvia the oxygen atom, Q is a hydrogen, halogen alkyl or alkenyl radical,p is an integer of from 1 to 5, and z is an integer at least equal to 2.9. The claim 8 process, wherein R'''' is phenylene, X is a chloride,--OEO-- is of the formula: ##STR19## wherein independently each R is asdefined hereinbefore, R' is hydrogen and R" is phenylene.
 10. The claim9 process, wherein c is equal to 2, the sum of a plus b is 40 to 170,both x and y are equal to 1, and z is equal to 2 to
 1000. 11. The claim10 process, wherein each R is hydrogen, a hydrocarbon, or ahalohydrocarbon radical.
 12. The claim 11 process, wherein each R is amethyl radical.
 13. The claim 8, 9, 10, 11 or 12 process, carried out inthe presence of water soluble base.
 14. The claim 13 process, carriedout in the presence of a catalytic phase transfer agent.